EP1250378B1 - Material for coatings and adhesives based on polymers comprising thioether structural units and method for producing said compounds - Google Patents
Material for coatings and adhesives based on polymers comprising thioether structural units and method for producing said compounds Download PDFInfo
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- EP1250378B1 EP1250378B1 EP00990664A EP00990664A EP1250378B1 EP 1250378 B1 EP1250378 B1 EP 1250378B1 EP 00990664 A EP00990664 A EP 00990664A EP 00990664 A EP00990664 A EP 00990664A EP 1250378 B1 EP1250378 B1 EP 1250378B1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J181/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Adhesives based on polysulfones; Adhesives based on derivatives of such polymers
- C09J181/04—Polysulfides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
- C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/12—Polythioether-ethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
- C09D181/04—Polysulfides
Definitions
- the invention relates to a novel substance for the production of coatings and bonds based on polymers with thioether structural units and a novel method for its production.
- Coatings and bonds are used on a large scale and in a variety of ways.
- the application spectrum ranges from protective layers for material surfaces to decorative coatings and also includes the bonding of various materials such as glass, plastics and metals.
- the properties of the polymers used for the coatings and bonds must be matched precisely to the respective application and to the material to be coated or bonded. Of particular importance are the adaptation of the thermomechanical properties of the polymers to the materials to be coated or glued or to the application effect to be achieved with the coating or gluing, the lowest possible shrinkage in the curing reaction and high adhesion to the material surfaces.
- the use of prepolymers can largely influence the properties of polymers made from them, such as flexibility, adhesion or shrinkage.
- polymers for coatings and adhesives should have high transparency and long-term UV and climate stability. After curing, which takes place in the shortest possible time and with the least possible shrinkage, the surfaces must not be sticky.
- the production of the starting components should be synthetically simple, reproducible and inexpensive.
- a number of coating materials or adhesives are used, the starting components of which are wholly or partly based on prepolymers or oligomers.
- Patent WO 96/12749 describes a silane oligomer of the general formula (R 3 ) -X- (R 1 x ) -Y-Si (R 2 ) 3 for coating glass surfaces, where R 3 is a polymerizable group, R 1 x the backbone oligomer with a molecular weight> 200, R 2 represents a hydrolyzable group and X or Y coupling groups.
- the coatings show sufficient adhesion to glass surfaces and increase the resistance of the glass to water or reduce the water absorption of the glass.
- the hydrolyzable groups in particular create good adhesion to the glass surface.
- a non-polar backbone ensures reduced water absorption.
- polymerizable groups used are thiol-ene or amine-ene systems and cationic ring-opening epoxides.
- the backbone oligomer produced in a preliminary stage can consist of a polyolefin, polyether, polyester or polycarbonate or also their copolymers.
- polyolefin polyether
- polyester polycarbonate
- urethanes were also produced and used for this by basic catalysis.
- the silane oligomer is reacted with other reactive oligomers or reactive diluents.
- suitable photo or cationic initiators coating materials obtained with a low glass point and good mechanical properties.
- No. 4,243,793 discloses prepolymers for photochemically curing coatings by reacting aliphatic diisocyanates with isocyanate end groups and an alkyl side chain with an olefinically unsaturated compound containing hydroxyl, mercapto or amino groups.
- This unsaturated prepolymer is provided with a photoinitiator and optionally a polymercaptan for the production of photo-curing coatings.
- Attempts are made to eliminate the previously known shortcomings of photochemically curing systems. This was mainly due to the too long reaction times, the complicated compositions due to often exotic and expensive components.
- the application of the coating materials is followed by curing with UV light in the wavelength range from 200 nm to 400 nm in 0.1 seconds to 20 minutes at temperatures from 0 ° to 100 ° C., preferably at 20 ° C. to 40 ° C. , Transparent or opaque coatings are obtained.
- German patent DE 19 809 643 A1 describes coating compositions and adhesives, their use and processes for their production.
- the formulations consist of a binder, a crosslinking agent and a C 7 -C 16 alkane which is functionalized with at least two hydroxyl or thiol groups or at least one hydroxyl and thiol group.
- This is intended to provide coating compositions or adhesives which have an increased solids content compared to those known hitherto and are low in emissions.
- the described type of formulation is intended to remedy the disadvantages of the reactive thinners used, such as the dissolving of additional lacquer layers during application, the lowering of the thermostability and the light resistance. But at the same time, the materials are said to be improved Show scratch resistance and good reflow behavior.
- the binder should form three-dimensional networks with the crosslinker.
- the binder can have any number of functional groups, but preferably those such as the functionalized alkane.
- hydroxy-functionalized polyacrylates polyesters, polyurethanes, acrylated polyurethanes, acrylated polyesters, polylactones, polycarbonates, polyethers and / or (meth) acrylate diols are used. All substances which can react with hydroxyl groups are suitable as crosslinkers. Examples are compounds containing siloxane groups, anhydrides or polyisocyanates. Common auxiliaries and / or additives are added to the coating materials. These are slip additives, defoamers, polymerization inhibitors, matting agents, leveling agents and film-forming aids.
- the coating compositions or adhesives are preferably formulated as non-aqueous solutions or dispersions with organic solvents.
- a liquid radiation-curing coating system is described in US 4,120,721.
- an acrylate or methacrylate-terminated urethane prepolymer with a non-water-soluble vinyl monomer thinner preferably an acrylate or methacrylate, a polythiol, which contains at least two thiol groups per molecule and a photoinitiator is described.
- the polythioether synthesis is initiated by light in the wavelength range from 200 to 400 nm.
- US Pat. No. 4,017,371 discloses solid styrene-allyl alcohol copolymers which, when mixed with liquid polythiols, cure to form polyene-polythiol systems, primarily for photoresist applications.
- the solid polyenes can also be reacted with unsaturated isocyanates.
- the object of the invention is therefore to provide a technically simple to carry out and economically and ecologically rational process for producing a material for coatings and bonds, which is suitable for the coating and bonding of glass, plastics and metals, and one for to show the coating and bonding required material, a targeted adjustment of the thermo-technical properties is possible and the disadvantages of the known technical solutions are eliminated.
- the coatings and bonds produced using the new process should also have a high level of transparency and high adhesive strength, as well as climate and UV stability.
- the required properties should be achieved with a sufficient dripping time from the solvent-free starting components within a short time in the range of a few minutes, a few seconds or shorter and without the need to use a protective gas atmosphere.
- the object is achieved according to the invention in that coatings and bonds are produced on the basis of polymers with thioether structural units.
- R 4 ⁇ CH 2 ⁇ CH 2 ⁇ O ⁇ CH 2 ⁇ CH 2 ⁇ O ⁇ CH 2 ⁇ CH 2 -
- An essential part of the invention is the production of the thiol-functionalized prepolymers.
- the thiol functionality is generated by the base-catalyzed addition of dithiols with diisocyanates to form thiocarbamate structures.
- the reaction to form the polymers according to the invention can be carried out either thermally or photochemically.
- the reaction is preferably carried out photochemically.
- azo compounds e.g. ⁇ , ⁇ '-azoisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-amidinopropane) dihydrochloride or peroxides, such as dibenzoyl peroxide in an amount of 0.01-3, 0 wt .-% used.
- the photochemical production of the coatings and bonds according to the invention is advantageously carried out in the wavelength range between 250 nm and 700 nm.
- Compounds such as hydroxyketones, for example 1-hydroxy-cyclohexylphenyl ketone, monoacylphosphines, for example 2,4,6-trimethylbenzoylbisphenylphosphine oxide, for example bisacylphosphines, are used as photoinitiators Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, benzoyl derivatives, e.g. 2-hydroxy-2-methyl-1-phenylpropan-2-one, Benzophenone used in an amount of 0.01 to 3.5 wt .-% alone or in a mixture.
- suitable light stabilizers such as e.g. Bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2-hydroxyphenylbenzotriazoles, 2-hydroxybenzophenones, 2-hydroxyphenyltriazines are mixed in an amount of 0.01 to 5% by weight.
- the coatings and bonds according to the invention are advantageously produced from solvent-free reaction mixtures.
- solvents suitable for dilution such as e.g. Acetone, chloroform, butyl acetate can be added.
- the coatings and bonds according to the invention are produced by applying mixtures of the components to the material to be coated or bonded by means of customary coating techniques, such as spraying, dipping, knife coating, spinning, manual and / or semi-automatic and / or fully automatic metering technology, and then curing them.
- customary coating techniques such as spraying, dipping, knife coating, spinning, manual and / or semi-automatic and / or fully automatic metering technology, and then curing them.
- the coatings and bonds according to the invention are characterized in that the mechanical properties of the polymers according to the invention can be varied from hard to soft-flexible by structural variation of the starting components and / or their molar ratios in the reaction mixture and by variation of the parameters of photocuring or thermal curing. They can therefore be used in a variety of ways for transparent, low-shrinkage, protective and decorative coatings on glass, plastics and metals as well as for bonding. They show excellent climate and UV stability as well as adhesion to the materials mentioned.
- the curing time of the coatings according to the invention in particular in the case of light curing, is in the range from 3 minutes to 5 minutes, so that short, previously impossible production times can be achieved.
- the dripping time of the mixture of substances is in the range of 2 days, so that unproblematic and flexible handling of the resin with the appropriate dosing technology and use in manual, mechanical and automated systems is guaranteed.
- the coatings of the invention adhere to polyester and PVC films, to glass and to metallic surfaces.
- the resins according to the invention are suitable for the coating of film surfaces, whereby screen printing, color transfer printing or thermal sublimation printing is possible, so that they can be used in all common digital printing processes. Reference is made once again to the conventional coating techniques already mentioned above.
- the UV and external resistance determined correspond to the VDA standards.
- 1.5 mol of the thiol-functional prepolymer P1 thus prepared are mixed with a mol of 2,4,6-triallyloxy-1,3,5-triazine, a% by weight from a mixture of bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate and 1-methyl-8- (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (Tinuvin 292) and 1.5% by weight Darocur 1173 (registered trademark) mixed homogeneously. After degassing, the mixture is applied by knife coating to the surface to be coated. The curing takes place in 20 seconds with a UV lamp, which has a radiation intensity of greater than 80 m 3 / cm 2 , to form a flexible coating.
- a UV lamp which has a radiation intensity of greater than 80 m 3 / cm 2 , to form a flexible coating.
- the prepolymer P 1 is produced as described in Example 1.
- a second basic component is produced to increase liability.
- a suitable reaction vessel one mole of pentaerythritol tetrakis (3-mercaptopropionic acid) with one mole of phenyl isocyanate and 500 ml of dry Toluene mixed. After adding 0.02-0.05% by weight of DABCO, the mixture is stirred at room temperature for 24 hours. After filtration through silica gel, the solvent is drawn off on a rotary evaporator and dried to constant weight.
- the reaction product S4P thus produced is used for the coating materials.
- All of the coating mixtures described in the exemplary embodiments can also be used as adhesives for suitable glass-glass, glass-plastic or glass-metal bonds.
- the polymers according to the invention can also be prepared by thermal curing. If dibenzoyl peroxide is used, the curing times should be 30 to 180 minutes at temperatures of 60 ° C to 80 ° C.
- the present invention includes both a coating and adhesive material based on polymers having thioether structural units and a process for producing a coating material and adhesive based on polymers having thioether structural units.
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
Die Erfindung betrifft einen neuartigen Stoff zur Herstellung von Beschichtungen und Verklebungen auf der Basis von Polymeren mit Thioether-Struktureinheiten sowie ein neuartiges Verfahren zu seiner Herstellung.The invention relates to a novel substance for the production of coatings and bonds based on polymers with thioether structural units and a novel method for its production.
Beschichtungen und Verklebungen werden technisch in großem Umfang und in vielfältiger Weise genutzt. Das Anwendungsspektrum reicht von Schutzschichten für Werkstoffoberflächen bis hin zu dekorativen Beschichtungen und umfasst auch Verklebungen der unterschiedlichsten Materialien, wie Glas, Kunststoffe und Metalle. Die Eigenschaften der für die Beschichtungen und Verklebungen verwendeten Polymere müssen dabei genau auf den jeweiligen Anwendungszweck sowie auf das zu beschichtende oder zu verklebende Material abgestimmt werden. Von besonderer Bedeutung sind die Anpassung der thermomechanischen Eigenschaften der Polymere an die zu beschichtenden oder zu verklebenden Materialien bzw. an den mit der Beschichtung oder Verklebung zu erreichenden Anwendungseffekt, eine möglichst niedrige Schrumpfung bei der Härtungsreaktion sowie eine hohe Haftung auf den Materialoberflächen. Durch den Einsatz von Prepolymeren können die Eigenschaften von daraus hergestellten Polymeren, wie Flexibilität, Haftung oder auch die Schrumpfung weitgehend beeinflusst werden.Coatings and bonds are used on a large scale and in a variety of ways. The application spectrum ranges from protective layers for material surfaces to decorative coatings and also includes the bonding of various materials such as glass, plastics and metals. The properties of the polymers used for the coatings and bonds must be matched precisely to the respective application and to the material to be coated or bonded. Of particular importance are the adaptation of the thermomechanical properties of the polymers to the materials to be coated or glued or to the application effect to be achieved with the coating or gluing, the lowest possible shrinkage in the curing reaction and high adhesion to the material surfaces. The use of prepolymers can largely influence the properties of polymers made from them, such as flexibility, adhesion or shrinkage.
Darüber hinaus besteht aus ökonomischer und ökologischer Sicht die Forderung nach kurzen Reaktionszeiten, insbesondere unter Nutzung von strahlungshärtenden, vorzugsweise photohärtenden Prozessen. Kurze Bestrahlungszeiten führen zu einer sehr vorteilhaften Energiebilanz und einem gutem Leistungsprofil. Außerdem sollen durch lösungsmittelfreies Arbeiten ökologische Schädigungen eingeschränkt werden.In addition, from an economic and ecological point of view, there is a demand for short reaction times, in particular using radiation-curing, preferably photo-curing processes. Short irradiation times lead to a very advantageous energy balance and a good performance profile. In addition, ecological damage should be limited by working without solvents.
Polymere für Beschichtungen und Verklebungen sollen außer den genannten Eigenschaften eine hohe Transparenz sowie eine Langzeit-UV- und Klimastabilität aufweisen. Nach der Härtung, die in möglichst kurzer Zeit und unter möglichst geringer Schrumpfung erfolgt, dürfen die Oberflächen nicht klebrig sein.In addition to the properties mentioned, polymers for coatings and adhesives should have high transparency and long-term UV and climate stability. After curing, which takes place in the shortest possible time and with the least possible shrinkage, the surfaces must not be sticky.
Die Herstellung der Ausgangskomponenten sollte synthetisch einfach, reproduzierbar und preiswert sein.The production of the starting components should be synthetically simple, reproducible and inexpensive.
In der Anwendung befinden sich eine Anzahl von Beschichtungsmaterialien oder Klebstoffen, deren Ausgangskomponenten ganz oder teilweise auf Prepolymeren oder Oligomeren basieren.A number of coating materials or adhesives are used, the starting components of which are wholly or partly based on prepolymers or oligomers.
So ist im Patent WO 96/12749 ein Silanoligomer der allgemeinen Formel (R3)-X-(R1 x)-Y-Si(R2)3, für die Beschichtung von Glasoberflächen beschrieben, wobei R3 eine polymerisierbare Gruppe, R1 x das Rückgrat-Oligomer mit einem Molekulargewicht > 200, R2 eine hydrolysierbare Gruppe und X bzw. Y Kopplungsgruppen darstellen. Die Beschichtungen zeigen eine ausreichende Haftung auf Glasoberflächen und erhöhen die Beständigkeit des Glases gegen Wasser bzw. verringern die Wasseraufnahme des Glases. Besonders durch die hydrolysierbaren Gruppen wird die gute Haftung auf der Glasoberfläche erzeugt. Ein nicht polares Rückgrat sorgt für die reduzierte Wasseraufnahme. Als polymerisierbare Gruppen werden neben radikalisch reagierenden Systemen, wie Acrylaten, Methacrylaten, Vinylethern oder Acrylamiden auch Thiol-En- bzw. Amin-En-Systeme sowie kationisch ringöffnende Epoxide eingesetzt. Das in einer Vorstufe hergestellte Rückgrat-Oligomer kann aus einem Polyolefin, Polyether, Polyester oder Polycarbonat bzw. auch deren Copolymeren bestehen. Durch den Einsatz von entsprechenden Polyolen und Isocyanaten wurden hierfür durch basische Katalyse auch Urethane hergestellt und verwendet. Das Silan-Oligomer wird mit anderen reaktiven Oligomeren oder Reaktivverdünnern zur Reaktion gebracht. Durch die Verwendung geeigneter Photo- oder kationischer Initiatoren werden Beschichtungsmaterialien mit niedrigem Glaspunkt und guten mechanischen Eigenschaften erhalten.Patent WO 96/12749 describes a silane oligomer of the general formula (R 3 ) -X- (R 1 x ) -Y-Si (R 2 ) 3 for coating glass surfaces, where R 3 is a polymerizable group, R 1 x the backbone oligomer with a molecular weight> 200, R 2 represents a hydrolyzable group and X or Y coupling groups. The coatings show sufficient adhesion to glass surfaces and increase the resistance of the glass to water or reduce the water absorption of the glass. The hydrolyzable groups in particular create good adhesion to the glass surface. A non-polar backbone ensures reduced water absorption. In addition to radical-reacting systems such as acrylates, methacrylates, vinyl ethers or acrylamides, polymerizable groups used are thiol-ene or amine-ene systems and cationic ring-opening epoxides. The backbone oligomer produced in a preliminary stage can consist of a polyolefin, polyether, polyester or polycarbonate or also their copolymers. By using appropriate polyols and isocyanates, urethanes were also produced and used for this by basic catalysis. The silane oligomer is reacted with other reactive oligomers or reactive diluents. By using suitable photo or cationic initiators, coating materials obtained with a low glass point and good mechanical properties.
Die Herstellungsprozedur stellt sich jedoch als sehr umfangreich und mehrstufig dar.However, the manufacturing procedure is very extensive and multi-stage.
In der US 4,243,793 werden Prepolymere für photochemisch härtende Beschichtungen durch Reaktion von aliphatischen Diisocyanaten mit Isocyanat-Endgruppen und einer Alkylseitenkette mit einer hydroxy-, mercapto- oder aminogruppenhaltigen olefinisch ungesättigten Verbindung offenbart. Dieses ungesättigte Prepolymer wird mit einem Photoinitiator und wahlweise einem Polymercaptan zur Herstellung photohärtender Beschichtungen versehen. Es wird versucht, die bisher bekannten Mängel photochemisch härtender Systeme zu beseitigen. Diese lagen vor allem in den zu langen Reaktionszeiten, den komplizierten Zusammensetzungen durch oft exotische und teure Komponenten begründet. Der nach verschiedenen Methoden durchgeführten Applikation der Beschichtungsmaterialien folgt die Härtung mit UV-Licht im Wellenlängenbereich von 200 nm bis 400 nm in 0,1 Sekunden bis 20 Minuten bei Temperaturen von 0° bis 100°C, vorzugsweise bei 20°C bis 40°C. Es werden transparente oder opake Beschichtungen erhalten.No. 4,243,793 discloses prepolymers for photochemically curing coatings by reacting aliphatic diisocyanates with isocyanate end groups and an alkyl side chain with an olefinically unsaturated compound containing hydroxyl, mercapto or amino groups. This unsaturated prepolymer is provided with a photoinitiator and optionally a polymercaptan for the production of photo-curing coatings. Attempts are made to eliminate the previously known shortcomings of photochemically curing systems. This was mainly due to the too long reaction times, the complicated compositions due to often exotic and expensive components. The application of the coating materials, carried out according to various methods, is followed by curing with UV light in the wavelength range from 200 nm to 400 nm in 0.1 seconds to 20 minutes at temperatures from 0 ° to 100 ° C., preferably at 20 ° C. to 40 ° C. , Transparent or opaque coatings are obtained.
In dem deutschen Patent DE 19 809 643 Al werden Beschichtungsmittel und Klebstoffe, ihre Verwendung und Verfahren zu ihrer Herstellung beschrieben. Die Formulierungen bestehen aus einem Bindemittel, einem Vernetzer und einem C7-C16-Alkan, das mit mindestens zwei Hydroxyl- oder Thiolgruppen oder mindestens einer Hydroxyl- und Thiolgruppe funktionalisiert ist. Hiermit sollen Beschichtungsmittel oder Klebstoffe zur Verfügung gestellt werden, die gegenüber den bisher bekannten einen erhöhten Feststoffgehalt aufweisen und emissionsarm sind. Durch die beschriebene Art der Formulierung sollen die Nachteile von verwendeten Reaktivverdünnern, wie das Anlösen weiterer Lackschichten bei der Applikation, die Erniedrigung der Thermostabilität und die Lichtbeständigkeit behoben werden. Aber gleichzeitig sollen die Materialien eine verbesserte Kratzfestigkeit und ein gutes Reflow-Verhalten zeigen. Das Bindemittel soll mit dem Vernetzer dreidimensionale Netzwerke bilden. Hierfür kann das Bindemittel beliebig viele funktionelle Gruppen, vorzugsweise aber solche wie das funktionalisierte Alkan aufweisen. Es werden besonders hydroxyfunktionalisierte Polyacrylate, Polyester, Polyurethane, acrylierte Polyurethane, acrylierte Polyester, Polylactone, Polycarbonate, Polyether und/oder (Meth-) Acrylatdiole eingesetzt. Als Vernetzer kommen hierbei alle Substanzen, die mit Hydroxylgruppen reagieren können in Betracht. Beispiele sind siloxangruppenhaltige Verbindungen, Anhydride oder Polyisocyanate. Den Beschichtungsmaterialien werden übliche Hilfsmittel und/oder Additive zugesetzt. Dies sind Slipadditive, Entschäumer, Polymerisationsinhibitoren, Mattierungsmittel, Verlaufsmittel und filmbildende Hilfsmittel. Die Beschichtungsmittel oder Klebstoffe werden vorzugsweise als nichtwässrige Lösungen oder Dispersionen mit organischen Lösungsmitteln formuliert.German patent DE 19 809 643 A1 describes coating compositions and adhesives, their use and processes for their production. The formulations consist of a binder, a crosslinking agent and a C 7 -C 16 alkane which is functionalized with at least two hydroxyl or thiol groups or at least one hydroxyl and thiol group. This is intended to provide coating compositions or adhesives which have an increased solids content compared to those known hitherto and are low in emissions. The described type of formulation is intended to remedy the disadvantages of the reactive thinners used, such as the dissolving of additional lacquer layers during application, the lowering of the thermostability and the light resistance. But at the same time, the materials are said to be improved Show scratch resistance and good reflow behavior. The binder should form three-dimensional networks with the crosslinker. For this purpose, the binder can have any number of functional groups, but preferably those such as the functionalized alkane. In particular, hydroxy-functionalized polyacrylates, polyesters, polyurethanes, acrylated polyurethanes, acrylated polyesters, polylactones, polycarbonates, polyethers and / or (meth) acrylate diols are used. All substances which can react with hydroxyl groups are suitable as crosslinkers. Examples are compounds containing siloxane groups, anhydrides or polyisocyanates. Common auxiliaries and / or additives are added to the coating materials. These are slip additives, defoamers, polymerization inhibitors, matting agents, leveling agents and film-forming aids. The coating compositions or adhesives are preferably formulated as non-aqueous solutions or dispersions with organic solvents.
Der Nachteil dieser Verbindungen liegt in ihrer Aushärtung, die auf thermischem Weg bei Temperaturen von vorzugsweise 60°C bis 180°C erfolgt.The disadvantage of these compounds lies in their curing, which takes place thermally at temperatures of preferably 60 ° C. to 180 ° C.
Ein flüssiges strahlungshärtendes Beschichtungssystem wird in der US 4,120,721 beschrieben. Hier wird ein acrylat- oder methacrylatterminiertes Urethan-Prepolymer mit einem nicht wasserlöslichen Vinylmonomer-Verdünner, vorzugsweise einem Acrylat oder Methacrylat, einem Polythiol, welches mindestens zwei Thiolgruppen pro Molekül enthält und einem Photoinitiator beschrieben. Die Polythioether-Synthese wird durch Licht im Wellenlängenbereich von 200 bis 400 nm initiiert.A liquid radiation-curing coating system is described in US 4,120,721. Here, an acrylate or methacrylate-terminated urethane prepolymer with a non-water-soluble vinyl monomer thinner, preferably an acrylate or methacrylate, a polythiol, which contains at least two thiol groups per molecule and a photoinitiator is described. The polythioether synthesis is initiated by light in the wavelength range from 200 to 400 nm.
In der US 4,017,371 werden feste Styren-Allylalkohol-Copolymere offenbart, die in der Mischung mit flüssigen Polythiolen zu Polyen-Polythiol-Systemen, vorwiegend für Photoresist-Anwendungen, aushärten. Die festen Polyene können auch mit ungesättigten Isocyanaten zur Reaktion gebracht werden.US Pat. No. 4,017,371 discloses solid styrene-allyl alcohol copolymers which, when mixed with liquid polythiols, cure to form polyene-polythiol systems, primarily for photoresist applications. The solid polyenes can also be reacted with unsaturated isocyanates.
Ein entscheidender Nachteil dieses Patentes liegt in der Aushärtung mit radioaktiver Strahlung. Aber auch der Einsatz dieses bereits festen vorgebildeten Polyens stellt für die Löslichkeit in weiteren Folgeschritten eine Schwierigkeit dar.A decisive disadvantage of this patent is the curing with radioactive radiation. However, the use of this already solid, pre-formed polyene also poses a problem for the solubility in further subsequent steps.
Aus den genannten Gründen können die bekannten technischen Lösungen nicht alle von der Technik gestellten Forderungen erfüllen.For the reasons mentioned, the known technical solutions cannot meet all the demands made by technology.
Die Aufgabe der Erfindung ist es daher, ein technisch einfach durchzuführendes sowie ökonomisch und ökologisch rationelles Verfahren zur Herstellung eines Stoffs für von Beschichtungen und Verklebungen zur Verfügung zu stellen, das für die Beschichtung und Verklebung von Glas, Kunststoffen und Metallen geeignet ist, sowie einen für die Beschichtung und Verklebung erforderlichen Stoff aufzuzeigen, wobei eine gezielte Einstellung der thermomechnischen Eigenschaften möglich ist und die Nachteile der bekannten technischen Lösungen beseitigt werden.The object of the invention is therefore to provide a technically simple to carry out and economically and ecologically rational process for producing a material for coatings and bonds, which is suitable for the coating and bonding of glass, plastics and metals, and one for to show the coating and bonding required material, a targeted adjustment of the thermo-technical properties is possible and the disadvantages of the known technical solutions are eliminated.
Die nach dem neuen Verfahren hergestellten Beschichtungen und Verklebungen sollen darüber hinaus eine hohe Transparenz sowie eine hohe Haftfestigkeit, Klima- und UV-Stabilität aufweisen. Die geforderten Eigenschaften sollen bei einer ausreichenden Tropfzeit aus den lösungsmittelfreien Ausgangskomponenten innerhalb kurzer Zeit im Bereich von einigen Minuten, einigen Sekunden oder kürzer und ohne eine notwendige Anwendung einer Schutzgasatmosphäre erreicht werden.The coatings and bonds produced using the new process should also have a high level of transparency and high adhesive strength, as well as climate and UV stability. The required properties should be achieved with a sufficient dripping time from the solvent-free starting components within a short time in the range of a few minutes, a few seconds or shorter and without the need to use a protective gas atmosphere.
Die Aufgabe wird erfindungsgemäß dadurch gelöst, dass Beschichtungen und Verklebungen auf Basis von Polymeren mit Thioether-Struktureinheiten hergestellt werden. Dazu werden olefinische Verbindungen mit der allgemeinen Struktur
(CH2=CR1)n-R2 n = 2; 3; 4 R1 = H; CH3
R2 =
HS-R 4 -S-CO-NH-R 5 -NH-CO-S-R 4 -SH
R 4 =
―CH 2 ―CH 2 ―O―CH 2 ―CH 2 ―O―CH 2 ―CH 2 ―
R 5 =
―CH 2 ―CH 2 ―CH 2 ―CH 2 ―CH 2 ―CH 2 ―
(HS) n -R 6 n = 2; 3; 4
R6 =
―CH 2 ―CH 2 ―O―CH 2 ―CH 2 ―O―CH 2 ―CH 2 ―
(CH 2 = CR 1 ) n -R 2 n = 2; 3; 4 R 1 = H; CH 3
R 2 =
HS-R 4 -S-CO-NH-R 5 -NH-CO-SR 4 -SH
R 4 =
―CH 2 ―CH 2 ―O ― CH 2 ―CH 2 ―O ― CH 2 ―CH 2 -
R 5 =
―CH 2 ―CH 2 ―CH 2 ―CH 2 ―CH 2 ―CH 2 -
(HS) n -R 6 n = 2; 3; 4
R 6 =
―CH 2 ―CH 2 ―O ― CH 2 ―CH 2 ―O ― CH 2 ―CH 2 -
Ein wesentlicher Bestandteil der Erfindung ist die Herstellung der thiolfunktionalisierten Prepolymere. Die Thiolfunktionalität wird dabei durch die basisch katalysierte Addition von Dithiolen mit Diisocyanaten unter Bildung von Thiocarbamatstrukturen erzeugt.An essential part of the invention is the production of the thiol-functionalized prepolymers. The thiol functionality is generated by the base-catalyzed addition of dithiols with diisocyanates to form thiocarbamate structures.
Die Reaktion zur Bildung der erfindungsgemäßen Polymeren kann sowohl thermisch oder photochemisch initiiert durchgeführt werden. Vorzugsweise erfolgt die Reaktion photochemisch.The reaction to form the polymers according to the invention can be carried out either thermally or photochemically. The reaction is preferably carried out photochemically.
Bei thermischer Initiierung der Reaktion werden zweckmäßig Temperaturen zwischen 20°C und 100°C angewendet. Als thermische Initiatoren werden an sich bekannte Verbindungen wie Azo-Verbindungen, z.B. α,α'-Azoisobutyronitril, 2,2'-Azobis-(2,4-dimethylvaleronitril), 2,2'-Azobis-(2-amidinopropan)dihydrochlorid oder Peroxide, wie Dibenzoylperoxid in einer Menge von 0,01 - 3,0 Gew.-% verwendet.When the reaction is initiated thermally, temperatures between 20 ° C. and 100 ° C. are expediently used. Compounds known per se, such as azo compounds, e.g. α, α'-azoisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-amidinopropane) dihydrochloride or peroxides, such as dibenzoyl peroxide in an amount of 0.01-3, 0 wt .-% used.
Die photochemische Herstellung der erfindungsgemäßen Beschichtungen und Verklebungen erfolgt vorteilhaft im Wellenlängenbereich zwischen 250 nm und 700 nm. Dabei werden als Photoinitiatoren Verbindungen wie Hydroxyketone, z.B. 1-Hydroxy-cyclohexyl-phenylketon, Monoacylphosphine, z.B. 2,4,6-Trimethylbenzoylbisphenylphosphinoxid, Bisacylphosphine, z.B. Bis(2,4,6-trimethylbenzoyl)phenylphosphinoxid, Benzoylderivate, z.B. 2-Hydroxy-2-methyl-1-phenylpropan-2-on, Benzophenon in einer Menge von 0,01 bis 3,5 Gew.-% allein oder in Mischung verwendet.The photochemical production of the coatings and bonds according to the invention is advantageously carried out in the wavelength range between 250 nm and 700 nm. Compounds such as hydroxyketones, for example 1-hydroxy-cyclohexylphenyl ketone, monoacylphosphines, for example 2,4,6-trimethylbenzoylbisphenylphosphine oxide, for example bisacylphosphines, are used as photoinitiators Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, benzoyl derivatives, e.g. 2-hydroxy-2-methyl-1-phenylpropan-2-one, Benzophenone used in an amount of 0.01 to 3.5 wt .-% alone or in a mixture.
Zur Verbesserung der UV-Stabilität der Beschichtungen und Verklebungen können in die Reaktionsmischungen geeignete Lichtschutzmittel, wie z.B. Bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacat, 2-Hydroxyphenylbenzotriazole, 2-Hydroxybenzophenone, 2-Hydroxyphenyltriazine in einer Menge von 0,01 bis 5 Gew.-% eingemischt werden.In order to improve the UV stability of the coatings and bonds, suitable light stabilizers, such as e.g. Bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2-hydroxyphenylbenzotriazoles, 2-hydroxybenzophenones, 2-hydroxyphenyltriazines are mixed in an amount of 0.01 to 5% by weight.
Die erfindungsgemäßen Beschichtungen und Verklebungen werden vorteilhaft aus lösungsmittelfreien Reaktionsmischungen erzeugt. Zur Erzeugung geringer Schichtdicken oder wenn die Anwendung niedrigviskose Reaktionsmischungen erfordert, können zur Verdünnung geeignete Lösungsmittel, wie z.B. Aceton, Chloroform, Butylacetat zugesetzt werden.The coatings and bonds according to the invention are advantageously produced from solvent-free reaction mixtures. In order to produce thin layers or if the application requires low-viscosity reaction mixtures, solvents suitable for dilution, such as e.g. Acetone, chloroform, butyl acetate can be added.
Die erfindungsgemäßen Beschichtungen und Verklebungen werden hergestellt, indem Mischungen der Komponenten mittels gebräuchlicher Beschichtungstechniken, wie Sprühen, Tauchen, Rakeln, Schleudern, manueller und/oder halbautomatischer und/oder vollautomatischer Dosiertechnik auf das zu beschichtende oder zu verklebende Material aufgebracht und anschließend gehärtet werden.The coatings and bonds according to the invention are produced by applying mixtures of the components to the material to be coated or bonded by means of customary coating techniques, such as spraying, dipping, knife coating, spinning, manual and / or semi-automatic and / or fully automatic metering technology, and then curing them.
Die erfindungsgemäßen Beschichtungen und Verklebungen zeichnen sich dadurch aus, dass durch strukturelle Variation der Ausgangskomponenten und/oder ihrer Molverhältnisse in der Reaktionsmischung sowie durch Variation der Parameter der Photohärtung oder der thermischen Härtung die mechanischen Eigenschaften der erfindungsgemäßen Polymere von hart bis weich-flexibel variierbar sind. Sie können daher in vielfältiger Weise für transparente, schrumpfungsarme, schützende und dekorative Beschichtungen auf Glas, Kunststoffen und Metallen sowie für Verklebungen verwendet werden. Sie zeigen eine ausgezeichnete Klima- und UV-Stabilität sowie Haftung auf den genannten Materialien.The coatings and bonds according to the invention are characterized in that the mechanical properties of the polymers according to the invention can be varied from hard to soft-flexible by structural variation of the starting components and / or their molar ratios in the reaction mixture and by variation of the parameters of photocuring or thermal curing. They can therefore be used in a variety of ways for transparent, low-shrinkage, protective and decorative coatings on glass, plastics and metals as well as for bonding. They show excellent climate and UV stability as well as adhesion to the materials mentioned.
Die Aushärtezeit der erfindungsgemäßen Beschichtungen liegen, insbesondere bei Lichthärtung, im Bereich von 3 Minuten bis 5 Minuten, so dass kurze, bisher nicht mögliche Fertigungszeiten erreicht werden können.The curing time of the coatings according to the invention, in particular in the case of light curing, is in the range from 3 minutes to 5 minutes, so that short, previously impossible production times can be achieved.
Die Tropfzeit der Stoffmischung liegt hierbei im Bereich von 2 Tagen, so dass eine unproblematische und flexible Handhabung des Harzes mit einer entsprechenden Dosiertechnik und der Einsatz in manuellen, maschinellen und automatisierten Anlagen gewährleistet ist.The dripping time of the mixture of substances is in the range of 2 days, so that unproblematic and flexible handling of the resin with the appropriate dosing technology and use in manual, mechanical and automated systems is guaranteed.
Die erfindungsgemäßen Beschichtungen haften auf Polyester- und PVC-Folien, auf Glas und auf metallischen Oberflächen.The coatings of the invention adhere to polyester and PVC films, to glass and to metallic surfaces.
Die erfindungsgemäßen Harze sind für die Beschichtung von Folienoberflächen geeignet, wobei Siebdruck, Farbtransferdruck oder Thermosublimationsdruck möglich ist, so dass ein Einsatz in allen gängigen Digitaldruckverfahren denkbar ist. Auf die bereits oben genannten konventionellen Beschichtungstechniken wird nochmals verwiesen.The resins according to the invention are suitable for the coating of film surfaces, whereby screen printing, color transfer printing or thermal sublimation printing is possible, so that they can be used in all common digital printing processes. Reference is made once again to the conventional coating techniques already mentioned above.
Die festgestellten UV- und Außenbeständigkeiten entsprechen den VDA-Normen.The UV and external resistance determined correspond to the VDA standards.
Im folgenden wird die Erfindung an einigen Ausführungsbeispielen näher erläutert.The invention is explained in more detail below using a few exemplary embodiments.
In einem geeigneten Reaktionsgefäß werden unter Ausschluss von Feuchtigkeit 2 mol 3,6-Dioxaoctan-1,8-dithiol und 1 mol 1,6-Diisoocyanato-2,2(4),4-trimethylhexan homogen vermischt. Dazu wird unter Rühren 0,002 - 0,005 Gew.-% 1,4-Diazabicyclo[2,2,2]octan (DABCO) gegeben. Die Reaktion verläuft unter Erwärmung und Zunahme der Viskosität. Es muss darauf geachtet werden, dass die Reaktionstemperatur 60°C bis 80°C nicht übersteigt. Eventuell muss gekühlt werden. Es wird das Prepolymer P1 erhalten.In a suitable reaction vessel, 2 moles of 3,6-dioxaoctane-1,8-dithiol and 1 mole of 1,6-diisoocyanato-2,2 (4), 4-trimethylhexane are mixed homogeneously with the exclusion of moisture. For this, 0.002-0.005% by weight of 1,4-diazabicyclo [2.2.2] octane (DABCO) is added with stirring. The reaction proceeds with heating and increasing viscosity. Care must be taken to ensure that the reaction temperature does not exceed 60 ° C to 80 ° C. You may need to cool. The prepolymer P1 is obtained.
Von dem so hergestellten thiolfunktionellen Prepolymer P1 werden 1,5 mol mit einem mol 2,4,6-Triallyloxy-1,3,5-triazin, einem Gew.-% aus einer Mischung von Bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-sebacat und 1-Methyl-8-(1,2,2,6,6-pentamethyl-4-piperidinyl)-sebacat (Tinuvin 292) und 1,5 Gew.-% Darocur 1173 (eingetragene Marke) homogen vermischt. Nach den Entgasen wird die Mischung durch Rakeln auf die zu beschichtende Oberfläche aufgetragen. Die Härtung erlfolgt mit einer UV-Lampe, die eine Strahlungsintensität von größer 80 m3/cm2 besitzt, in 20 Sekunden zu einer flexiblen Beschichtung.1.5 mol of the thiol-functional prepolymer P1 thus prepared are mixed with a mol of 2,4,6-triallyloxy-1,3,5-triazine, a% by weight from a mixture of bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate and 1-methyl-8- (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (Tinuvin 292) and 1.5% by weight Darocur 1173 (registered trademark) mixed homogeneously. After degassing, the mixture is applied by knife coating to the surface to be coated. The curing takes place in 20 seconds with a UV lamp, which has a radiation intensity of greater than 80 m 3 / cm 2 , to form a flexible coating.
Zu einem mol Prepolymer P1, welches wie unter Ausführungsbeispiel 1 beschrieben hergestellt wurde, werden 0,25 mol Pentaerythritoltetrakis-(3-mercaptopropionsäure), ein mol 1,3,5-Triallyl-1,3,5-triazin-2,4,6(1H,3H,5H)-trion, ein Gew.-% Tinuvin 292, ein Gew.-% einer Mischung aus 2-[4-((2-Hydroxy-3-didecyoxypropyl)-oxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin und 2-[4-((2-Hydroxy-3-tridecyoxypropyl)-oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin (Tinuvin 400), zwei Gew.-% Irgacur 1700 (eingetragene Marke) gegeben und homogen vermischt. Nach dem Entgasen wird das Beschichtungsmaterial mit halbautomatischer Dosiertechnik aufgetragen und mit der unter Ausführungsbeispiel 1 beschriebenen UV-Lampe 30 Sekunden bestrahlt. Die Beschichtungen sind flexibel, transparent und UV stabil.0.25 mol of pentaerythritol tetrakis (3-mercaptopropionic acid), one mol of 1,3,5-triallyl-1,3,5-triazine-2,4, are added to one mole of prepolymer P1, which was prepared as described in Example 1, 6 (1H, 3H, 5H) -trione, a% by weight of Tinuvin 292, a% by weight of a mixture of 2- [4 - ((2-hydroxy-3-didecyoxypropyl) -oxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and 2- [4 - ((2-hydroxy-3-tridecyoxypropyl) -oxy] -2-hydroxyphenyl] -4,6- bis (2,4-dimethylphenyl) -1,3,5-triazine (Tinuvin 400), two% by weight Irgacur 1700 (registered trademark) and mixed homogeneously. After degassing, the coating material is applied with semi-automatic dosing technology and with the Irradiated for 30 seconds as described in embodiment 1. The coatings are flexible, transparent and UV stable.
Die Herstellung des Prepolymeren P 1 erfolgt wie unter Ausführungsbeispiel 1 beschrieben. Zur Erhöhung der Haftung wird eine zweite Grundkomponente hergestellt. In einem geeigneten Reaktionsgefäß wird unter Feuchtigkeitsausschluss ein mol Pentaerythritoltetrakis-(3-mercaptopropionsäure) mit einem mol Phenylisocyanat und 500 ml trockenem Toluol vermischt. Nach Zugabe von 0,02-0,05 Gew.-% DABCO wird 24 Stunden bei Raumtemperatur gerührt. Nach Filtration über Kieselgel wird das Lösungsmittel am Rotationsverdampfer abgezogen und bis zur Gewichtskonstanz getrocknet. Das so hergestellte Reaktionsprodukt S4P wird für die Beschichtungsmaterialien eingesetzt.
Es werden 0,5 mol S4P, 0,25 mol des Prepolymeren P1, 0,25 mol Pentaerythritoltetrakis-(3-mercaptopropionsäure), ein Gew.-% Tinuvin 292, ein Gew.-% Tinuvin 400 mit 1,5 Gew.-% Irgacur 1700 (eingetragene Marke) gemischt und entgast. Mit manueller Dosiertechnik werden die Beschichtungsmaterialien aufgetragen und in 20 Sekunden mit der unter Ausführungsbeispiel 1 beschriebenen UV-Lampe bestrahlt.The prepolymer P 1 is produced as described in Example 1. A second basic component is produced to increase liability. In a suitable reaction vessel, one mole of pentaerythritol tetrakis (3-mercaptopropionic acid) with one mole of phenyl isocyanate and 500 ml of dry Toluene mixed. After adding 0.02-0.05% by weight of DABCO, the mixture is stirred at room temperature for 24 hours. After filtration through silica gel, the solvent is drawn off on a rotary evaporator and dried to constant weight. The reaction product S4P thus produced is used for the coating materials.
0.5 mol of S4P, 0.25 mol of the prepolymer P1, 0.25 mol of pentaerythritol tetrakis (3-mercaptopropionic acid), a% by weight of Tinuvin 292, a% by weight of Tinuvin 400 with 1.5% by weight % Irgacur 1700 (registered trademark) mixed and degassed. The coating materials are applied using manual dosing technology and irradiated in 20 seconds with the UV lamp described in embodiment 1.
In einem geeigneten Reaktionsgefäß werden unter Ausschluss von Feuchtigkeit zwei mol 3,6-Dioxaoctan-1,8-dithiol und ein mol Isophorondiisocyanat vermischt. Dazu wird unter Rühren 0,002-0,005 Gew.-% DABCO gegeben. Die Reaktion verläuft unter Erwärmung und Zunahme der Viskosität. Es muss darauf geachtet werden, dass die Reaktionstemperatur 60°C bis 80°C nicht übersteigt. Gegebenenfalls muss gekühlt werden. Das so erhaltene Prepolymer P2 ist thiolfunktionalisiert.
Es werden 1,5 mol Prepolymer P2, ein mol 1,3,5-Triallyl-1,3,5-triazin-2,4,6(1H,3H,5H)-trion, ein Gew.-% Tinuvin 292, ein Gew.-% Tinuvin 400 und 0,5 Gew.-% Darocur 1173 vermischt und entgast. Nach manuellem Auftragen der Beschichtung wird 10 Sekunden und nach 30 Sekunden Pause weitere 90 Sekunden mit der unter Ausführungsbeispiel 1 beschriebenen UV-Lampe bestrahlt. Der entstehende Film ist transparent, aber deutlich härter als die in den Ausführungsbeispielen 1 bis 3 beschriebenen.Two moles of 3,6-dioxaoctane-1,8-dithiol and one mole of isophorone diisocyanate are mixed in a suitable reaction vessel with the exclusion of moisture. For this, 0.002-0.005% by weight of DABCO is added with stirring. The reaction proceeds with heating and increasing viscosity. Care must be taken to ensure that the reaction temperature does not exceed 60 ° C to 80 ° C. Cooling may be necessary. The prepolymer P2 thus obtained is thiol-functionalized.
1.5 mol of prepolymer P2, one mol of 1,3,5-triallyl-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, a% by weight of Tinuvin 292, a wt .-% Tinuvin 400 and 0.5 wt .-% Darocur 1173 mixed and degassed. After manual application of the coating, the UV lamp described in embodiment 1 is irradiated for a further 10 seconds and after a 30-second pause. The resulting film is transparent, but significantly harder than that described in working examples 1 to 3.
Alle in den Ausführungsbeispielen beschriebenen Beschichtungsmischungen können auch als Klebstoffe für geeignete Glas-Glas-, Glas-Kunstoff- oder Glas-Metall-Verklebungen eingesetzt werden.All of the coating mixtures described in the exemplary embodiments can also be used as adhesives for suitable glass-glass, glass-plastic or glass-metal bonds.
Durch den Austausch des Photoinitiators durch einem thermischen Initiator, wie beispielsweise Dibenzoylperoxid, sind die erfindungsgemäßen Polymere auch durch eine thermische Härtung herstellbar. Im Falle der Verwendung von Dibenzoylperoxid sollten die Härtungszeiten 30 bis 180 Minuten bei Temperaturen von 60°C bis 80°C betragen.By replacing the photoinitiator with a thermal initiator, such as, for example, dibenzoyl peroxide, the polymers according to the invention can also be prepared by thermal curing. If dibenzoyl peroxide is used, the curing times should be 30 to 180 minutes at temperatures of 60 ° C to 80 ° C.
Aus obigem geht hervor, daß die vorliegende Erfindung sowohl einen Stoff für Beschichtungen und Verklebungen auf der Basis von Polymeren mit Thioether-Struktureinheiten als auch ein Verfahren zum Herstellen eines Stoffs für Beschichtungen und Verklebungen auf der Basis von Polymeren mit Thioether-Struktureinheiten umfaßt.From the above, it can be seen that the present invention includes both a coating and adhesive material based on polymers having thioether structural units and a process for producing a coating material and adhesive based on polymers having thioether structural units.
Claims (17)
- Material for coatings and adhesives based on polymers with thioether structural units,
characterized in that
olefinic compounds with the general structure
(CH2=CR1)n-R2 n = 2; 3; 4 R1 = H; CH3
R2 =
HS-R4-S-CO-NH-R5-NH-CO-S-R4-SH
R4 =
-CH2-CH2-O-CH2-CH2-O-CH2-CH2-
R5 =
-CH2-CH2-CH2-CH2-CH2-CH2-
(HS)n-R6 n = 2; 3; 4
R6 =
-CH2-CH2-O-CH2-CH2-O-CH2-CH2-
- Material for coatings and adhesives according to claim 1,
characterized in that
the reaction components are in a mixing ratio of olefinic component : thiol component : thiol-terminated prepolymer in a molar ratio of up to 1 : 0.9 : 0.1. - Material for coatings and adhesives according to claim 1 or 2,
characterized in that
thermal initiators, that is to say azo compounds chosen from α,α*-azoisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile) and 2,2'-azobis-(2-amidinopropane) dihydrochloride, or dibenzoyl peroxide, are used in an amount of 0.01 - 3.0 wt.%. - Material for coatings and adhesives according to claim 1 to 3,
characterized in that
the reaction is carried out using photoinitiators, that is to say hydroxy-ketones, chosen from 1-hydroxy-cyclohexyl phenyl ketone, monoacylphosphines, chosen from 2,4,6-trimethylbenzoylbisphenylphosphine oxide, bisacylphosphines, chosen from bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and benzoyl derivatives, chosen from 2-hydroxy-2-methyl-1-phenylpropan-2-one and benzophenone, in an amount of 0.01 to 3.5 wt.%, by themselves or in a mixture. - Material for coatings and adhesives according to claim 1 to 4,
characterized in that
light stabilizers, chosen from bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2-hydroxyphenylbenzotriazoles, 2-hydroxy-benzophenones and 2-hydroxyphenyltriazines, are used in an amount of 0.01 to 5 wt.%. - Material for coatings and adhesives according to claim 1 to 5,
characterized in that
the components are applied by means of conventional coating techniques, such as spraying, dipping, knife-coating, whirler coating or a manual and/or semi-automatic and/or completely automatic metering technique, to the material to be coated or to be glued. - Process for the preparation of a material for coatings and adhesives based on polymers with thioether structural units,
characterized in that
olefinic compounds with the general structure
(CH2=CR1)n-R2 n = 2; 3; 4 R1 = H; CH3
R2 =
HS-R4-S-CO-NH-R5-NH-CO-S-R4-SH
R4 =
- CH2-CH2-O-CH2-CH2-O-CH2-CH2-
R5 =
-CH2-CH2-CH2-CH2-CH2-CH2-
(HS)n-R6 n = 2; 3; 4
R6 =
-CH2-CH2-O-CH2-CH2-O-CH2-CH2-
- Process according to claim 7,
characterized in that
the reaction components are in a mixing ratio of olefinic component : thiol component : thiol-terminated prepolymer in a molar ratio of up to 1 : 0.9 : 0.1. - Process according to claim 7 or 8,
characterized in that
the reaction is carried out thermally or photochemically. - Process according to claim 7 to 9,
characterized in that
the reaction is carried out thermally in the temperature range from 20°C to 100°C. - Process according to claim 7 to 9,
characterized in that
the reaction is carried out photochemically in the wavelength range from 250 nm to 700 nm. - Process according to claim 7 to 10,
characterized in that
the components are applied by means of conventional coating techniques, such as spraying, dipping, knife-coating, whirler coating or a manual and/or semi-automatic and/or completely automatic metering technique, to the material to be coated or to be glued. - Process according to claim 7 to 9,
characterized in that
the reaction is carried out using photoinitiators, that is to say hydroxy-ketones, chosen from 1-hydroxy-cyclohexyl phenyl ketone, monoacylphosphines, chosen from 2,4,6-trimethylbenzoylbisphenylphosphine oxide, bisacylphosphines, chosen from bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and benzoyl derivatives, chosen from 2-hydroxy-2-methyl-1-phenylpropan-2-one and benzophenone, in an amount of 0.01 to 3.5 wt.%, by themselves or in a mixture. - Process according to claim 7 to 10,
characterized in that
light stabilizers, chosen from bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2-hydroxyphenylbenzotriazoles, 2-hydroxy-benzophenones and 2-hydroxyphenyltriazines, are used in an amount of 0.01 to 5 wt.%. - Process according to claim 7 to 14,
characterized in that acetone, chloroform or butyl acetate is used for the dilution. - Process according to claim 7 to 11,
characterized in that
the components are applied by means of conventional coating techniques, such as spraying, dipping, knife-coating, whirler coating or a manual and/or semi-automatic and/or completely automatic metering technique, to the material to be coated or to be glued. - Use of a material for coatings and adhesives according to one of patent claims 1 to 6,
characterized in that
the material is employed for coating of materials such that these materials are self-adhesive after the coating.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19959134 | 1999-12-08 | ||
| DE19959134 | 1999-12-08 | ||
| DE10028358A DE10028358A1 (en) | 1999-12-08 | 2000-06-08 | Material for coatings and bonds based on polymers with thioether structural units and process for its production |
| DE10028358 | 2000-06-08 | ||
| PCT/EP2000/012309 WO2001042382A2 (en) | 1999-12-08 | 2000-12-06 | Material for coatings and adhesives based on polymers comprising thioether structural units and method for producing said compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1250378A2 EP1250378A2 (en) | 2002-10-23 |
| EP1250378B1 true EP1250378B1 (en) | 2004-03-31 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP00990664A Expired - Lifetime EP1250378B1 (en) | 1999-12-08 | 2000-12-06 | Material for coatings and adhesives based on polymers comprising thioether structural units and method for producing said compounds |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP1250378B1 (en) |
| AU (1) | AU3007101A (en) |
| WO (1) | WO2001042382A2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2873015C (en) | 2012-03-21 | 2018-11-13 | Bradley Fixtures Corporation | Basin and hand drying system |
| WO2015011147A1 (en) * | 2013-07-22 | 2015-01-29 | Ceramtec-Etec Gmbh | Transparent adhesive with a refractive index ranging from 1.7 to 1.73 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3872151A (en) * | 1970-05-26 | 1975-03-18 | Clifton L Kehr | Polyene carbamates |
| US3877971A (en) * | 1973-10-25 | 1975-04-15 | Grace W R & Co | Photocurable polyene-polythiol compositions containing the adduct of diallylmalate and toluene diisocyanate |
| US3996257A (en) * | 1974-09-09 | 1976-12-07 | W. R. Grace & Co. | Polythiocarbamate monomers |
| JPS6049716B2 (en) * | 1977-06-11 | 1985-11-05 | 昭和高分子株式会社 | Substrate surface treatment method for imparting conductivity |
-
2000
- 2000-12-06 WO PCT/EP2000/012309 patent/WO2001042382A2/en active IP Right Grant
- 2000-12-06 EP EP00990664A patent/EP1250378B1/en not_active Expired - Lifetime
- 2000-12-06 AU AU30071/01A patent/AU3007101A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| WO2001042382A2 (en) | 2001-06-14 |
| EP1250378A2 (en) | 2002-10-23 |
| WO2001042382A3 (en) | 2002-01-10 |
| AU3007101A (en) | 2001-06-18 |
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